JP7416720B2 - Method for preparing fluorinated peroxide - Google Patents
Method for preparing fluorinated peroxide Download PDFInfo
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- JP7416720B2 JP7416720B2 JP2020558584A JP2020558584A JP7416720B2 JP 7416720 B2 JP7416720 B2 JP 7416720B2 JP 2020558584 A JP2020558584 A JP 2020558584A JP 2020558584 A JP2020558584 A JP 2020558584A JP 7416720 B2 JP7416720 B2 JP 7416720B2
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- 238000000034 method Methods 0.000 title claims description 31
- 150000002978 peroxides Chemical class 0.000 title description 10
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 31
- 229910052731 fluorine Inorganic materials 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 24
- 239000011737 fluorine Substances 0.000 claims description 22
- 229910021608 Silver(I) fluoride Inorganic materials 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 18
- KWVVTSALYXIJSS-UHFFFAOYSA-L silver(ii) fluoride Chemical compound [F-].[F-].[Ag+2] KWVVTSALYXIJSS-UHFFFAOYSA-L 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- VMUWIFNDNXXSQA-UHFFFAOYSA-N hypofluorite Chemical compound F[O-] VMUWIFNDNXXSQA-UHFFFAOYSA-N 0.000 claims description 9
- 238000006552 photochemical reaction Methods 0.000 claims description 9
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Inorganic materials [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 8
- 229910001506 inorganic fluoride Inorganic materials 0.000 claims description 8
- IYRWEQXVUNLMAY-UHFFFAOYSA-N carbonyl fluoride Chemical compound FC(F)=O IYRWEQXVUNLMAY-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- GFADZIUESKAXAK-UHFFFAOYSA-N tetrafluorohydrazine Chemical compound FN(F)N(F)F GFADZIUESKAXAK-UHFFFAOYSA-N 0.000 claims description 6
- 210000002268 wool Anatomy 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical class FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 claims description 5
- 229910021593 Copper(I) fluoride Inorganic materials 0.000 claims description 4
- 101100328843 Dictyostelium discoideum cofB gene Proteins 0.000 claims description 4
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 2
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 claims description 2
- 229910016509 CuF 2 Inorganic materials 0.000 claims description 2
- 229910021587 Nickel(II) fluoride Inorganic materials 0.000 claims description 2
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 2
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 claims description 2
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- LLLVXZXLTMTLQX-UHFFFAOYSA-N fluorohydrazine Chemical compound NNF LLLVXZXLTMTLQX-UHFFFAOYSA-N 0.000 claims 1
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 27
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 229940096017 silver fluoride Drugs 0.000 description 7
- SYNPRNNJJLRHTI-UHFFFAOYSA-N 2-(hydroxymethyl)butane-1,4-diol Chemical compound OCCC(CO)CO SYNPRNNJJLRHTI-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- OMRRUNXAWXNVFW-UHFFFAOYSA-N fluoridochlorine Chemical compound ClF OMRRUNXAWXNVFW-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- -1 peroxide compounds Chemical class 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- XZNOAVNRSFURIR-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-ol Chemical compound FC(F)(F)C(O)(C(F)(F)F)C(F)(F)F XZNOAVNRSFURIR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910001504 inorganic chloride Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- JOHWNGGYGAVMGU-UHFFFAOYSA-N trifluorochlorine Chemical compound FCl(F)F JOHWNGGYGAVMGU-UHFFFAOYSA-N 0.000 description 2
- RMHJZXQCOUCQQX-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-[1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-yl]peroxy-2-(trifluoromethyl)propane Chemical compound FC(F)(F)C(C(F)(F)F)(C(F)(F)F)OOC(C(F)(F)F)(C(F)(F)F)C(F)(F)F RMHJZXQCOUCQQX-UHFFFAOYSA-N 0.000 description 1
- COLOHWPRNRVWPI-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound [CH2]C(F)(F)F COLOHWPRNRVWPI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910020323 ClF3 Inorganic materials 0.000 description 1
- 101100441092 Danio rerio crlf3 gene Proteins 0.000 description 1
- JNCMHMUGTWEVOZ-UHFFFAOYSA-N F[CH]F Chemical compound F[CH]F JNCMHMUGTWEVOZ-UHFFFAOYSA-N 0.000 description 1
- 108010081348 HRT1 protein Hairy Proteins 0.000 description 1
- 102100021881 Hairy/enhancer-of-split related with YRPW motif protein 1 Human genes 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- BHIMBOXMFLXMGZ-UHFFFAOYSA-N [1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-yl] hypofluorite Chemical compound FOC(C(F)(F)F)(C(F)(F)F)C(F)(F)F BHIMBOXMFLXMGZ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- VUWZPRWSIVNGKG-UHFFFAOYSA-N fluoromethane Chemical compound F[CH2] VUWZPRWSIVNGKG-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 231100000935 short-term exposure limit Toxicity 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/12—Fluorides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
- B01J37/26—Fluorinating
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
- C07C409/16—Peroxy compounds the —O—O— group being bound between two carbon atoms not further substituted by oxygen atoms, i.e. peroxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本出願は、欧州特許出願公開第１８ １６９ １９４．０号に対する優先権を主張するものであり、この出願の全内容は、あらゆる目的のために参照により本明細書に組み込まれる。 This application claims priority to European Patent Application No. 18 169 194.0, the entire contents of which are incorporated herein by reference for all purposes.
本発明は、カルボニルフルオリド（ＣＯＦ２）の使用を回避する、過フッ素化された又は部分的にフッ素化された過酸化物の調製に関する。 The present invention relates to the preparation of perfluorinated or partially fluorinated peroxides that avoid the use of carbonyl fluoride ( COF2 ).
フッ素化過酸化物が知られている。例えば、ＣＦ３－Ｏ－Ｏ－ＣＦ３は、誘電絶縁ガスとして、ＳＦ６及びＮ２の代替として国際公開第２０１４／０９６４１４号パンフレットに記載されており、その製造は、米国特許出願公開第２００７／００４９７７４号明細書に記載されている。欧州特許出願公開第３ ０７８ ６５７号明細書及び同第３ ３０９ １４７号明細書は、両方とも特定のフッ素化過酸化物化合物及びそれらの調製方法を開示している。例えば、これらの文献は、適切なカルボニルフルオリド及び分子フッ素間の反応、適切なカルボニルフルオリド、ＣＯＦ２及び分子フッ素間の反応並びに適切なカルボニルフルオリド、オキシフルオリド及び分子フッ素間の反応を開示している。しかし、それらに記載の製造方法は、試薬としてカルボニルフルオリド（ＣＯＦ２及び／又は他の適切なカルボニルフルオリド）を使用する。カルボニルフルオリドは、短期暴露の限界値が２ｐｐｍで非常に有毒であると説明されており、水と激しく反応し、且つ高価である。更に、米国特許第４，０７５，０７３号明細書は、テトラフルオロヒドラジンＮ２Ｆ４の存在下でペルフルオロ－ｔ－ブチルハイポフルオライトを光分解することにより、ビス（ペルフルオロ－ｔ－ブチル）ペルオキシドを合成する方法について開示している。テトラフルオロヒドラジンは、フッ素原子スカベンジャーであり、これは、調製することが難しく、非常に危険であり、有機材料の存在下で爆発することが知られている。 Fluorinated peroxides are known. For example, CF 3 -O-O-CF 3 is described in WO 2014/096414 as an alternative to SF 6 and N 2 as a dielectric insulating gas, and its manufacture is described in US Patent Application Publication No. 2007 /0049774. EP 3 078 657 and EP 3 309 147 both disclose certain fluorinated peroxide compounds and methods for their preparation. For example, these documents disclose reactions between suitable carbonyl fluorides and molecular fluorine, reactions between suitable carbonyl fluorides, COF2 and molecular fluorine, and reactions between suitable carbonyl fluorides, oxyfluorides and molecular fluorine. are doing. However, the preparation methods described therein use carbonyl fluoride (COF 2 and/or other suitable carbonyl fluoride) as a reagent. Carbonyl fluoride is described as highly toxic with a short-term exposure limit of 2 ppm, reacts violently with water, and is expensive. Furthermore, U.S. Pat. No. 4,075,073 discloses that bis(perfluoro-t-butyl) peroxide is prepared by photolyzing perfluoro-t-butylhypofluorite in the presence of tetrafluorohydrazine N2F4 . Discloses a method for synthesizing. Tetrafluorohydrazine is a fluorine atom scavenger that is difficult to prepare, extremely dangerous, and known to be explosive in the presence of organic materials.
したがって、過フッ素化された及び部分的にフッ素化された過酸化物の改善された製造方法が依然として必要とされている。 Therefore, there remains a need for improved methods of making perfluorinated and partially fluorinated peroxides.
本発明の目的は、過フッ素化された又は部分的にフッ素化された過酸化物の改善された調製方法を提供することである。本発明により、この目的及び他の目的が達成される。本発明の方法は、改善された収率、改善された純度、改善された選択性、改善された安全性プロファイル、改善された商品コスト及び／又は改善されたエネルギー消費の点で有利である。 It is an object of the present invention to provide an improved method for the preparation of perfluorinated or partially fluorinated peroxides. This and other objectives are achieved by the present invention. The process of the invention is advantageous in improved yield, improved purity, improved selectivity, improved safety profile, improved cost of goods and/or improved energy consumption.
したがって、本発明の第１の態様は、式Ｒ１Ｒ２Ｒ３Ｃ－Ｏ－Ｏ－ＣＲ４Ｒ５Ｒ６（式中、Ｒ１～Ｒ６は、Ｆ又は過フッ素化された若しくは部分的にフッ素化された直鎖若しくは分枝鎖のアルキル基から独立して選択される）の化合物の製造の方法であって、ハイポフルオライトＲ１Ｒ２Ｒ３ＣＯＦ若しくはＲ１Ｒ２Ｒ３ＣＯＦとＲ４Ｒ５Ｒ６ＣＯＦの混合物並びに／又はハイポクロライトＲ１Ｒ２Ｒ３ＣＯＣｌ若しくはＲ１Ｒ２Ｒ３ＣＯＣｌとＲ４Ｒ５Ｒ６ＣＯＣｌの混合物をＣＯＦ２の非存在下で反応させる工程を含む方法に関する。 Accordingly, a first aspect of the invention provides a compound of the formula R 1 R 2 R 3 C-O-O-CR 4 R 5 R 6 , where R 1 to R 6 are F or a perfluorinated or moiety independently selected from fluorinated straight-chain or branched alkyl groups), comprising the steps of: hypofluorite R 1 R 2 R 3 COF or R 1 R 2 R 3 A mixture of COF and R 4 R 5 R 6 COF and/or a mixture of hypochlorite R 1 R 2 R 3 COCl or a mixture of R 1 R 2 R 3 COCl and R 4 R 5 R 6 COCl in the absence of COF 2 The present invention relates to a method including a step of reacting.
用語「非存在下」は、反応を進行させるために反応混合物にＣＯＦ２が添加されないことであると理解されたい。しかしながら、例えば、初期の反応からの不純物又は本発明の方法で形成された副産物として、ＣＯＦ２の痕跡が存在することを除外するべきではない。 The term "in the absence" is understood to mean that no COF 2 is added to the reaction mixture to drive the reaction. However, it should not be excluded that traces of COF 2 are present, for example as impurities from the initial reaction or by-products formed in the method of the invention.
一実施形態によれば、本発明による方法は、ＣＯＦ２及びＦ２の非存在下で実施される。 According to one embodiment, the method according to the invention is carried out in the absence of COF 2 and F 2 .
別の実施形態によれば、本発明による方法は、任意のカルボニルフルオリドの非存在下、特に式Ｒ’Ｒ’’Ｒ’’’ＣＣ（Ｏ）Ｆ（式中、Ｒ’、Ｒ’’及びＲ’’’は、Ｆ又は過フッ素化された若しくは部分的にフッ素化された直鎖若しくは分枝鎖のアルキル基から独立して選択される）の任意のカルボニルフルオリドの非存在下で実施される。別の実施形態によれば、本発明による方法は、任意の非常に有害な化合物の非存在下、特に三フッ化塩素ＣｌＦ３の非存在下で実施される。 According to another embodiment, the process according to the invention is performed in the absence of any carbonyl fluoride, in particular of the formula R'R''R'''CC(O)F, where R', R'' and R''' are independently selected from F or a perfluorinated or partially fluorinated straight or branched alkyl group) in the absence of any carbonyl fluoride. Implemented. According to another embodiment, the process according to the invention is carried out in the absence of any highly harmful compounds, in particular in the absence of chlorine trifluoride ClF3 .
別の実施形態によれば、本発明による方法は、任意のフッ素原子スカベンジャーの非存在下、特にテトラフルオロヒドラジンＮ２Ｆ４の非存在下で実施される。 According to another embodiment, the process according to the invention is carried out in the absence of any fluorine atom scavenger, in particular in the absence of tetrafluorohydrazine N2F4 .
式Ｒ１Ｒ２Ｒ３Ｃ－Ｏ－Ｏ－ＣＲ４Ｒ５Ｒ６の化合物は、対称の過酸化物（すなわち、基Ｒ１Ｒ２Ｒ３Ｃ及びＣＲ４Ｒ５Ｒ６は、同一である）であり得る。この場合、本発明の方法に使用されるハイポフルオライト及び／又はハイポクロライトは、同一である、すなわち１種のタイプのみのハイポフルオライト及び／又はハイポクロライトが反応で使用される。このような対称の過酸化物を調製するための方法が好ましい。 Compounds of the formula R 1 R 2 R 3 C-O-O-CR 4 R 5 R 6 are symmetrical peroxides (i.e. the groups R 1 R 2 R 3 C and CR 4 R 5 R 6 are identical). ). In this case, the hypofluorite and/or hypochlorite used in the process of the invention are identical, ie only one type of hypofluorite and/or hypochlorite is used in the reaction. A method for preparing such symmetrical peroxides is preferred.
式Ｒ１Ｒ２Ｒ３Ｃ－Ｏ－Ｏ－ＣＲ４Ｒ５Ｒ６の化合物は、非対称（すなわち、基Ｒ１Ｒ２Ｒ３Ｃ及びＣＲ４Ｒ５Ｒ６は、異なる）でもあり得る。この場合、２つの異なるハイポフルオライト及び／又はハイポクロライトの混合物が本発明の方法に使用される。 Compounds of formula R 1 R 2 R 3 C-O-O-CR 4 R 5 R 6 may also be asymmetric (ie, the groups R 1 R 2 R 3 C and CR 4 R 5 R 6 are different). In this case, a mixture of two different hypofluorites and/or hypochlorites is used in the process of the invention.
好ましくは、Ｒ１～Ｒ６は、Ｆ、ＣＦ３、Ｃ２Ｆ５及びＣ３Ｆ８からなる群から独立して選択される。具体的には、調製される化合物は、（ＣＦ３）３Ｃ－Ｏ－Ｏ－ＣＦ３、（Ｃ２Ｆ５）（ＣＦ３）２Ｃ－Ｏ－Ｏ－ＣＦ３、（Ｃ２Ｆ５）２（ＣＦ３）Ｃ－Ｏ－Ｏ－ＣＦ３、（Ｃ２Ｆ５）３Ｃ－Ｏ－Ｏ－ＣＦ３、（ＣＦ３）３Ｃ－Ｏ－Ｏ－Ｃ（ＣＦ３）３、（Ｃ２Ｆ５）（ＣＦ３）２Ｃ－Ｏ－Ｏ－Ｃ（ＣＦ３）３、（Ｃ２Ｆ５）２（ＣＦ３）Ｃ－Ｏ－Ｏ－Ｃ（ＣＦ３）３、（Ｃ２Ｆ５）３Ｃ－Ｏ－Ｏ－Ｃ（ＣＦ３）３、（Ｃ２Ｆ５）（ＣＦ３）２Ｃ－Ｏ－Ｏ－Ｃ（Ｃ２Ｆ５）（ＣＦ３）２、（Ｃ２Ｆ５）２（ＣＦ３）Ｃ－Ｏ－Ｏ－Ｃ（Ｃ２Ｆ５）（ＣＦ３）２、（Ｃ２Ｆ５）３Ｃ－Ｏ－Ｏ－Ｃ（Ｃ２Ｆ５）（ＣＦ３）２、（Ｃ２Ｆ５）２（ＣＦ３）Ｃ－Ｏ－Ｏ－Ｃ（Ｃ２Ｆ５）２（ＣＦ３）、（Ｃ２Ｆ５）３Ｃ－Ｏ－Ｏ－Ｃ（Ｃ２Ｆ５）２（ＣＦ３）、（Ｃ２Ｆ５）３Ｃ－Ｏ－Ｏ－Ｃ（Ｃ２Ｆ５）３、（ｉ－Ｃ３Ｆ７）（ＣＦ３）２Ｃ－Ｏ－Ｏ－ＣＦ３、（ｉ－Ｃ３Ｆ７）２（ＣＦ３）Ｃ－Ｏ－Ｏ－ＣＦ３、（ｉ－Ｃ３Ｆ７）３Ｃ－Ｏ－Ｏ－ＣＦ３、（ｉ－Ｃ３Ｆ７）（ＣＦ３）２Ｃ－Ｏ－Ｏ－Ｃ（ＣＦ３）３、（ｉ－Ｃ３Ｆ７）２（ＣＦ３）Ｃ－Ｏ－Ｏ－Ｃ（ＣＦ３）３、（ｉ－Ｃ３Ｆ７）３Ｃ－Ｏ－Ｏ－Ｃ（ＣＦ３）３、（ｉ－Ｃ３Ｆ７）（ＣＦ３）２Ｃ－Ｏ－Ｏ－Ｃ（ｉ－Ｃ３Ｆ７）（ＣＦ３）２、（ｉ－Ｃ３Ｆ７）２（ＣＦ３）Ｃ－Ｏ－Ｏ－Ｃ（ｉ－Ｃ３Ｆ７）（ＣＦ３）２、（ｉ－Ｃ３Ｆ７）３Ｃ－Ｏ－Ｏ－Ｃ（ｉ－Ｃ３Ｆ７）（ＣＦ３）２、（ｉ－Ｃ３Ｆ７）２（ＣＦ３）Ｃ－Ｏ－Ｏ－Ｃ（ｉ－Ｃ３Ｆ７）２（ＣＦ３）、（ｉ－Ｃ３Ｆ７）３Ｃ－Ｏ－Ｏ－Ｃ（ｉ－Ｃ３Ｆ７）２（ＣＦ３）、（ｉ－Ｃ３Ｆ７）３Ｃ－Ｏ－Ｏ－Ｃ（ｉ－Ｃ３Ｆ７）３、（ｉ－Ｃ３Ｆ７）（ＣＦ３）（Ｃ２Ｆ５）Ｃ－Ｏ－Ｏ－ＣＦ３、（ｉ－Ｃ３Ｆ７）（ＣＦ３）（Ｃ２Ｆ５）Ｃ－Ｏ－Ｏ－Ｃ（ＣＦ３）３、（ｉ－Ｃ３Ｆ７）（ＣＦ３）（Ｃ２Ｆ５）Ｃ－Ｏ－Ｏ－Ｃ（ｉ－Ｃ３Ｆ７）（ＣＦ３）２、（ｉ－Ｃ３Ｆ７）（ＣＦ３）（Ｃ２Ｆ５）Ｃ－Ｏ－Ｏ－Ｃ（ｉ－Ｃ３Ｆ７）（Ｃ２Ｆ５）（ＣＦ３）、（ｉ－Ｃ３Ｆ７）（ＣＦ３）（Ｃ２Ｆ５）Ｃ－Ｏ－Ｏ－Ｃ（ｉ－Ｃ３Ｆ７）２（ＣＦ３）、（ｉ－Ｃ３Ｆ７）（ＣＦ３）（Ｃ２Ｆ５）Ｃ－Ｏ－Ｏ－Ｃ（ｉ－Ｃ３Ｆ７）３及びＣＦ（ＣＦ３）２－Ｏ－Ｏ－ＣＦ（ＣＦ３）２、ＣＦ３ＣＦ２－Ｏ－Ｏ－ＣＦ３ＣＦ２、ＣＦ３－Ｏ－Ｏ－ＣＦ３ＣＦ２、ＣＦ３－Ｏ－Ｏ－ＣＦ３からなる群から選択される。 Preferably, R 1 -R 6 are independently selected from the group consisting of F, CF 3 , C 2 F 5 and C 3 F 8 . Specifically, the compounds prepared include (CF 3 ) 3 C-O-O-CF 3 , (C 2 F 5 )(CF 3 ) 2 C-O-O-CF 3 , (C 2 F 5 ) 2 (CF 3 )C-O-O-CF 3 , (C 2 F 5 ) 3 C-O-O-CF 3 , (CF 3 ) 3 C-O-O-C(CF 3 ) 3 , ( C2F5 )( CF3 ) 2C -O-O - C( CF3 ) 3 , (C2F5) 2 ( CF3 )C-O-O-C ( CF3 ) 3 , ( C2 F 5 ) 3 C-O-O-C(CF 3 ) 3 , (C 2 F 5 )(CF 3 ) 2 C-O-O-C(C 2 F 5 )(CF 3 ) 2 , (C 2 F 5 ) 2 (CF 3 )C-O-O-C(C 2 F 5 )(CF 3 ) 2 , (C 2 F 5 ) 3 C-O-O-C(C 2 F 5 )(CF 3 ) 2 , (C 2 F 5 ) 2 (CF 3 )C-O-O-C(C 2 F 5 ) 2 (CF 3 ), (C 2 F 5 ) 3 C-O-O-C(C 2 F 5 ) 2 (CF 3 ), (C 2 F 5 ) 3 C-O-O-C(C 2 F 5 ) 3 , (i-C 3 F 7 )(CF 3 ) 2 C-O-O- CF 3 , (i-C 3 F 7 ) 2 (CF 3 )C-O-O-CF 3 , (i-C 3 F 7 ) 3 C-O-O-CF 3 , (i-C 3 F 7 )(CF 3 ) 2 C-O-O-C(CF 3 ) 3 , (i-C 3 F 7 ) 2 (CF 3 )C-O-O-C(CF 3 ) 3 , (i-C 3 F 7 ) 3 C-O-O-C(CF 3 ) 3 , (i-C 3 F 7 )(CF 3 ) 2 C-O-O-C(i-C 3 F 7 )(CF 3 ) 2 , (i-C 3 F 7 ) 2 (CF 3 )C-O-O-C(i-C 3 F 7 )(CF 3 ) 2 , (i-C 3 F 7 ) 3 C-O-O- C(i-C 3 F 7 )(CF 3 ) 2 , (i-C 3 F 7 ) 2 (CF 3 )C-O-O-C(i-C 3 F 7 ) 2 (CF 3 ), ( i-C 3 F 7 ) 3 C-O-O-C(i-C 3 F 7 ) 2 (CF 3 ), (i-C 3 F 7 ) 3 C-O-O-C(i-C 3 F 7 ) 3 , (i-C 3 F 7 ) (CF 3 ) (C 2 F 5 ) C-O-O-CF 3 , (i-C 3 F 7 ) (CF 3 ) (C 2 F 5 ) C-O-O-C(CF 3 ) 3 , (i-C 3 F 7 )(CF 3 )(C 2 F 5 )C-O-O-C(i-C 3 F 7 )(CF 3 ) 2 , (i-C 3 F 7 ) (CF 3 ) (C 2 F 5 ) C-O-O-C (i-C 3 F 7 ) (C 2 F 5 ) (CF 3 ), (i-C 3 F 7 )(CF 3 )(C 2 F 5 )C-O-O-C(i-C 3 F 7 ) 2 (CF 3 ), (i-C 3 F 7 )(CF 3 )(C 2 F 5 ) C-O-O-C(i-C 3 F 7 ) 3 and CF(CF 3 ) 2 -O-O-CF(CF 3 ) 2 , CF 3 CF 2 -O-O-CF 3 CF 2 , CF 3 -O-O-CF 3 CF 2 , CF 3 -O-O-CF 3 .
また、好ましくは、ハイポフルオライトＲ１Ｒ２Ｒ３ＣＯＦ及び／若しくはＲ４Ｒ５Ｒ６ＣＯＦ並びに／又はハイポクロライトＲ１Ｒ２Ｒ３ＣＯＣｌ及び／若しくはＲ４Ｒ５Ｒ６ＣＯＣｌは、無機フルオリド又は無機クロリドと、より好ましくはＡｇＦ、ＡｇＦ２、ＣｕＦ、ＣｕＦ２、ＢａＦ２、ＣｓＦ、ＮｉＦ２からなる群から選択される無機フルオリドと、より好ましくはＡｇＦ及びＡｇＦ２の混合物と反応される。 Preferably, hypofluorite R 1 R 2 R 3 COF and/or R 4 R 5 R 6 COF and/or hypochlorite R 1 R 2 R 3 COCl and/or R 4 R 5 R 6 COCl are an inorganic fluoride or an inorganic chloride, more preferably an inorganic fluoride selected from the group consisting of AgF, AgF2 , CuF, CuF2 , BaF2 , CsF, NiF2 , more preferably a mixture of AgF and AgF2 . Ru.
好ましい実施形態によれば、ＡｇＦ及びＡｇＦ２の混合物は、銀ウールを元素フッ素で処理することによって調製される。ＡｇＦ／ＡｇＦ２の混合物を調製する工程は、好ましくは、ステンレス鋼容器で実施され得る。好ましい実施形態によれば、ガス状フッ素は、圧力が好ましくは約２バールの値に監視されている間、銀ウールに少しずつ添加され得る。フッ素の消費量が１時間当たり数ミリバールまで低下したとき、フッ素の添加を停止することができる。この手順は、周囲温度で開始され得、温度は、１５０℃まで上昇され得る。フッ化銀触媒の調製には数日かかる場合がある。フッ素のおよそ９５モル％が消費されると、調製工程が完了すると考えられる。 According to a preferred embodiment, a mixture of AgF and AgF2 is prepared by treating silver wool with elemental fluorine. The process of preparing the AgF/AgF 2 mixture may preferably be carried out in a stainless steel vessel. According to a preferred embodiment, gaseous fluorine can be added in portions to the silver wool while the pressure is preferably monitored at a value of about 2 bar. The addition of fluorine can be stopped when the consumption of fluorine has fallen to a few millibars per hour. The procedure can be started at ambient temperature and the temperature can be increased to 150°C. Preparing the silver fluoride catalyst may take several days. The preparation process is considered complete when approximately 95 mole percent of the fluorine is consumed.
任意の理論に縛られることを望むものではないが、本発明者らは、上に開示された方法によって得られたフッ化銀材料が、ＣＯＦ２の非存在下において、ハイポフルオリド化合物を本発明による対応する過酸化物に問題なく変換する一方、商業的フッ化銀がより非効果的であると考えている。 Without wishing to be bound by any theory, the inventors believe that the silver fluoride material obtained by the method disclosed above is capable of absorbing hypofluoride compounds in the absence of COF2 . While converting successfully to the corresponding peroxides according to the invention, we believe that commercial silver fluoride is less effective.
１つの好ましい実施形態によれば、本発明の１つの目的は、式Ｒ１Ｒ２Ｒ３Ｃ－Ｏ－Ｏ－ＣＲ４Ｒ５Ｒ６の化合物の製造の方法であって、銀ウールを元素フッ素で処理することにより、ＡｇＦ／ＡｇＦ２の混合物を調製することを含む第１の工程と、次いで、ハイポフルオライトＲ１Ｒ２Ｒ３ＣＯＦ若しくはＲ１Ｒ２Ｒ３ＣＯＦとＲ４Ｒ５Ｒ６ＣＯＦの混合物並びに／又はハイポクロライトＲ１Ｒ２Ｒ３ＣＯＣｌ若しくはＲ１Ｒ２Ｒ３ＣＯＣｌとＲ４Ｒ５Ｒ６ＣＯＣｌの混合物をＣＯＦ２の非存在下で前記ＡｇＦ／ＡｇＦ２の混合物と反応させることを含む第２の工程とを含む方法を含む（Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６は、上記で開示された意味を有する）。 According to one preferred embodiment, one object of the invention is a process for the production of a compound of the formula R 1 R 2 R 3 C-O-O-CR 4 R 5 R 6 , which comprises A first step comprising preparing a mixture of AgF/AgF 2 by treatment with fluorine and then hypofluorite R 1 R 2 R 3 COF or R 1 R 2 R 3 COF and R 4 R 5 A mixture of R 6 COF and/or hypochlorite R 1 R 2 R 3 COCl or a mixture of R 1 R 2 R 3 COCl and R 4 R 5 R 6 COCl is added to the AgF/AgF 2 mixture in the absence of COF 2 . a second step comprising reacting the mixture (R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the meanings disclosed above).
この好ましい実施形態で使用される無機フルオリドは、より好ましくは、少なくとも化学量論量で使用され、すなわち、それは、触媒量でのみ存在するわけではない。触媒と異なり、無機フルオリド又はクロリドは、反応において恒久的な化学変化を受けており、好ましくは別の工程で回収及び再生される。好ましくは、ハイポフルオライトＲ１Ｒ２Ｒ３ＣＯＦ及び／若しくはＲ４Ｒ５Ｒ６ＣＯＦ並びに／又はハイポクロライトＲ１Ｒ２Ｒ３ＣＯＣｌ及び／若しくはＲ４Ｒ５Ｒ６ＣＯＣｌに対する無機フルオリドのモル比は、０．５よりも高く、より好ましくは０．６、０．７、０．８又は０．９よりも高く、最も好ましくは１．０よりも高い。有利には、それは、１．５よりも高い、更に２．５のモル比で過剰に使用することもできる。 The inorganic fluoride used in this preferred embodiment is more preferably used in at least a stoichiometric amount, ie it is not only present in catalytic amounts. Unlike the catalyst, the inorganic fluoride or chloride has undergone permanent chemical changes in the reaction and is preferably recovered and regenerated in a separate step. Preferably, the inorganic fluoride for hypofluorite R 1 R 2 R 3 COF and/or R 4 R 5 R 6 COF and/or hypochlorite R 1 R 2 R 3 COCl and/or R 4 R 5 R 6 COCl The molar ratio is higher than 0.5, more preferably higher than 0.6, 0.7, 0.8 or 0.9, most preferably higher than 1.0. Advantageously, it can also be used in excess with a molar ratio of higher than 1.5, even 2.5.
また、好ましくは、ハイポフルオライトＲ１Ｒ２Ｒ３ＣＯＦ及び／若しくはＲ４Ｒ５Ｒ６ＣＯＦ並びに／又はハイポクロライトＲ１Ｒ２Ｒ３ＣＯＣｌ及び／若しくはＲ４Ｒ５Ｒ６ＣＯＣｌは、光化学反応で反応され、より好ましくは、光化学反応は、２００～４００ｎｍの波長、最も好ましくは２００～３００ｎｍのＵＶ光での照射下で実施される。 Preferably, hypofluorite R 1 R 2 R 3 COF and/or R 4 R 5 R 6 COF and/or hypochlorite R 1 R 2 R 3 COCl and/or R 4 R 5 R 6 COCl are The reaction is carried out in a photochemical reaction, more preferably the photochemical reaction is carried out under irradiation with UV light of a wavelength of 200-400 nm, most preferably 200-300 nm.
用語「光化学反応」は、光、好ましくはＵＶ光の吸収によって引き起こされる化学反応を意味するものとする。 The term "photochemical reaction" shall mean a chemical reaction caused by absorption of light, preferably UV light.
本発明の１つの他の目的は、式Ｒ１Ｒ２Ｒ３Ｃ－Ｏ－Ｏ－ＣＲ４Ｒ５Ｒ６（式中、Ｒ１～Ｒ６は、Ｆ又は過フッ素化された若しくは部分的にフッ素化された直鎖若しくは分枝鎖のアルキル基からなる群から独立して選択される）の化合物の製造の方法であって、ハイポクロライトＲ１Ｒ２Ｒ３ＣＯＣｌ又はＲ１Ｒ２Ｒ３ＣＯＣｌとＲ４Ｒ５Ｒ６ＣＯＣｌの混合物を光化学反応で反応させる工程を含む方法である。 One other object of the invention is to provide a compound having the formula R 1 R 2 R 3 C-O-O-CR 4 R 5 R 6 , where R 1 to R 6 are F or perfluorinated or partially independently selected from the group consisting of linear or branched alkyl groups fluorinated in This method includes a step of reacting a mixture of R 3 COCl and R 4 R 5 R 6 COCl through a photochemical reaction.
ハイポクロライトＲ１Ｒ２Ｒ３ＣＯＣｌ及び／又はＲ４Ｒ５Ｒ６ＣＯＣｌは、商業的に入手することができ、好ましくは、これらは、アルコールＲ１Ｒ２Ｒ３ＣＯＨ及び／若しくはＲ４Ｒ５Ｒ６ＣＯＨ又はケトンＲ１Ｒ２Ｃ（Ｏ）及び／若しくはＲ３Ｒ４Ｃ（Ｏ）（式中、Ｒ１～Ｒ６は、Ｆ又は過フッ素化された若しくは部分的にフッ素化された直鎖若しくは分枝鎖のアルキル基からなる群から独立して選択される）の、ＡｇＦ、ＡｇＦ２、ＣｕＦ、ＣｕＦ２、ＢａＦ２、ＣｓＦ、ＮｉＦ２からなる群から選択される無機フルオリドとの、好ましくはＣｓＦとの反応及びその後、一フッ化塩素（ＣｌＦ）の存在下における反応で調製され得る。したがって、アルコールＲ１Ｒ２Ｒ３ＣＯＨ及び／若しくはＲ４Ｒ５Ｒ６ＣＯＨ又はケトンＲ１Ｒ２Ｃ（Ｏ）及び／若しくはＲ３Ｒ４Ｃ（Ｏ）は、第１の工程で無機フルオリド、好ましくはＣｓＦと反応されて、対応するＲ１Ｒ２Ｒ３ＣＯＣｓ及び／又はＲ４Ｒ５Ｒ６ＣＯＣｓを形成し、その後、これがＣｌＦと反応されて、対応するハイポクロライトを形成する。 Hypochlorites R 1 R 2 R 3 COCl and/or R 4 R 5 R 6 COCl are commercially available and preferably they are combined with the alcohols R 1 R 2 R 3 COH and/or R 4 R 5 R 6 COH or ketones R 1 R 2 C(O) and/or R 3 R 4 C(O) (wherein R 1 to R 6 are F or perfluorinated or partially fluorinated an inorganic fluoride selected from the group consisting of AgF, AgF 2 , CuF, CuF 2 , BaF 2 , CsF, NiF 2 Preferably with CsF and subsequent reaction in the presence of chlorine monofluoride (ClF). Therefore, the alcohols R 1 R 2 R 3 COH and/or R 4 R 5 R 6 COH or the ketones R 1 R 2 C(O) and/or R 3 R 4 C(O) are added to the inorganic fluoride in the first step. , preferably with CsF to form the corresponding R 1 R 2 R 3 COCs and/or R 4 R 5 R 6 COCs, which is then reacted with ClF to form the corresponding hypochlorite.
別の態様では、本発明は、式Ｒ１Ｒ２Ｒ３Ｃ－Ｏ－Ｏ－ＣＲ４Ｒ５Ｒ６（式中、Ｒ１～Ｒ６は、Ｆ又は過フッ素化された若しくは部分的にフッ素化された直鎖若しくは分枝鎖のアルキル基からなる群から独立して選択される）の化合物の製造の方法であって、ハイポフルオライトＲ１Ｒ２Ｒ３ＣＯＦ及び／又はＲ４Ｒ５Ｒ６ＣＯＦをＡｇＦ、ＡｇＦ２又はＡｇＦ及びＡｇＦ２の混合物と反応させる工程を含む方法に関する。好ましくは、ＡｇＦ、ＡｇＦ２又はＡｇＦ及びＡｇＦ２の混合物は、ハイポフルオライトＲ１Ｒ２Ｒ３ＣＯＦ及び／又はＲ４Ｒ５Ｒ６ＣＯＦと比較して１．０よりも高いモル比で使用される。 In another aspect, the invention provides compounds of the formula R 1 R 2 R 3 C-O-O-CR 4 R 5 R 6 , where R 1 to R 6 are F or perfluorinated or partially independently selected from the group consisting of fluorinated straight-chain or branched alkyl groups, comprising the steps of : 5 R 6 COF with AgF, AgF 2 or a mixture of AgF and AgF 2 . Preferably, AgF, AgF 2 or a mixture of AgF and AgF 2 is used in a molar ratio higher than 1.0 compared to the hypofluorite R 1 R 2 R 3 COF and/or R 4 R 5 R 6 COF. be done.
本発明に関連して、用語「含む」は、「からなる」の意味を含むことを意図する。本開示において、単数形の表記は、複数形を含むことが意図される。表現「．．．～．．．を含む」は、限界値を含むものとして理解されなければならない。 In the context of the present invention, the term "comprising" is intended to include the meaning "consisting of." In this disclosure, references to the singular are intended to include the plural. The expression "comprising" must be understood as inclusive.
本開示において、「アルキル」は、好ましくは、１～５個の炭素原子を有する直鎖又は分枝鎖の飽和炭化水素を指す。アルキル基の好ましい例は、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル及びｔｅｒｔ－ブチルである。 In this disclosure, "alkyl" preferably refers to a straight or branched chain saturated hydrocarbon having 1 to 5 carbon atoms. Preferred examples of alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
用語「過フッ素化されたアルキル」は、全ての水素原子がフッ素で置き換えられている、好ましくは１～５個の炭素原子を有する直鎖又は分枝鎖の飽和炭化水素を指す。好ましい例は、ＣＦ３、ＣＦ３ＣＦ２、ＣＦ３ＣＦ２ＣＦ２、（ＣＦ３）２ＣＦ、ＣＦ３ＣＦ２ＣＦ２ＣＦ２、ＣＦ３ＣＦ２（ＣＦ３）ＣＦ２、（ＣＦ３）３Ｃである。 The term "perfluorinated alkyl" refers to a straight or branched chain saturated hydrocarbon, preferably having 1 to 5 carbon atoms, in which all hydrogen atoms are replaced by fluorine. Preferred examples are CF3 , CF3CF2 , CF3CF2CF2 , ( CF3 ) 2CF , CF3CF2CF2CF2 , CF3CF2 ( CF3 ) CF2 , ( CF3 ). 3C .
用語「部分的にフッ素化されたアルキルは、少なくとも１個の水素原子がフッ素で置き換えられている、好ましくは１～５個の炭素原子を有する直鎖又は分枝鎖の飽和炭化水素を指す。好ましい例は、ＣＨ２Ｆ、ＣＨＦ２、ＣＦ３ＣＨ２、ＣＦ３ＣＨＦ、ＣＦ３ＣＨ２ＣＨ２、ＣＦ３ＣＦ２ＣＨ２、（ＣＦ３）２ＣＨである。 The term "partially fluorinated alkyl" refers to a straight-chain or branched saturated hydrocarbon, preferably having from 1 to 5 carbon atoms, in which at least one hydrogen atom is replaced by fluorine. Preferred examples are CH2F , CHF2 , CF3CH2 , CF3CHF , CF3CH2CH2 , CF3CF2CH2 , ( CF3 ) 2CH .
本発明に従って調製された化合物は、電気化学デバイス、より具体的には電子ディスプレイ又はエネルギー貯蔵及び放出デバイスにおける電解質成分として使用することができる。化合物は、以下の電気化学デバイスの１つにおける電解質成分として使用され得る：
－ エレクトロクロミックデバイス：車又は住宅用窓、日除け、眼鏡、
－ エレクトロクロミックフラットスクリーン：テレビ、タブレット、スマートフォン、接続デバイス、
－ 二次リチウム電池、リチウム－硫黄電池、リチウム－空気電池、ナトリウム電池、
－ 高電圧電池、
－ スーパーキャパシタ、特に電解質を使用する二重層スーパーキャパシタ、
－ ソーラーパネル又は有機型（ＯＰＶ）などのエネルギー発生機。
Compounds prepared according to the invention can be used as electrolyte components in electrochemical devices, more specifically electronic displays or energy storage and release devices. The compound can be used as an electrolyte component in one of the following electrochemical devices:
- Electrochromic devices: car or residential windows, sunshades, glasses,
- Electrochromic flat screens: TVs, tablets, smartphones, connected devices,
- Secondary lithium batteries, lithium-sulfur batteries, lithium-air batteries, sodium batteries,
- high voltage batteries,
- supercapacitors, especially double layer supercapacitors using electrolytes,
- Energy generators such as solar panels or organic solar panels (OPV).
好ましくは、電気化学デバイスは、リチウムイオン電池、リチウム－硫黄電池又はスーパーキャパシタであり得る。 Preferably, the electrochemical device may be a lithium ion battery, a lithium-sulfur battery or a supercapacitor.
本発明に従って調製された化合物は、誘電絶縁ガスとしてＳＦ６の代わりにも使用され得る。 Compounds prepared according to the invention can also be used in place of SF6 as dielectric insulating gas.
参照により本明細書に組み込まれるいずれかの特許、特許出願及び刊行物の開示が、用語を不明瞭にさせ得る程度まで本発明の記載と矛盾する場合、本記載が優先するものとする。 To the extent that the disclosure of any patent, patent application, or publication incorporated herein by reference conflicts with the description of the invention to the extent that it may obscure terminology, the present description shall control.
ここで、本発明は、実例として与えられ、いかなる方法でも本明細書又は特許請求の範囲を限定することを意図されていない実施例において更に説明される。 The invention will now be further illustrated in examples, which are given by way of illustration and are not intended to limit the scope of the specification or the claims in any way.
実施例１：フッ化銀（ＡｇＦ／ＡｇＦ２）触媒の調製
銀ウール（約２０ｇ）をステンレス鋼容器中において元素フッ素で処理した。ステンレス鋼ライン内の圧力を監視しながら、ステンレス鋼ガス分配ライン及びステンレス鋼容器のガス入口バルブを介して２バールの圧力まで少しずつガス状フッ素を銀ウールに添加した。フッ素ガスの消費速度に応じて、反応容器の温度を最初の周囲温度から１５０℃まで上昇させながら、この手順を続けた。フッ素の消費速度が１時間当たり数ミリバールまで低下したとき、フッ素の添加を停止させた。フッ素のおよそ９５モル％が消費されるまで、フッ化銀触媒の調製に数日かかった。過剰なフッ素を、ソーダライムで満たされたチューブを介して耐フッ素性ポンプシステムによって除去した。
Example 1: Preparation of silver fluoride (AgF/ AgF2 ) catalyst Silver wool (approximately 20 g) was treated with elemental fluorine in a stainless steel container. Gaseous fluorine was added to the silver wool in portions to a pressure of 2 bar via the stainless steel gas distribution line and the gas inlet valve of the stainless steel vessel while monitoring the pressure in the stainless steel line. This procedure was continued while increasing the temperature of the reaction vessel from the initial ambient temperature to 150° C. depending on the rate of consumption of fluorine gas. The fluorine addition was stopped when the consumption rate of fluorine had decreased to a few millibars per hour. It took several days to prepare the silver fluoride catalyst until approximately 95 mole percent of the fluorine was consumed. Excess fluorine was removed by a fluorine-resistant pump system via tubing filled with soda lime.
実施例２：ペルフルオロｔｅｒｔ－ブチルハイポフルオライト（（ＣＦ３）３Ｃ－ＯＦ）の調製
ペルフルオロｔｅｒｔ－ブタノール（４．２ｇ、１７．８ｍｍｏｌ）を、慎重に乾燥させたＣｓＦ（２００ｇ）を備えたステンレス鋼容器で凝縮し、室温に到達させた。容器を鋼ラインに接続する前に混合物を十分に振とうした。－７８℃において、圧力が３００ｍｂａｒに達し、フッ素がそれ以上消費されなくなるまで元素フッ素を少しずつ添加した。－７８℃で更に２０分後、容器を－１９６℃に保持しながら、過剰なフッ素を除去した。
Example 2: Preparation of perfluoro tert-butyl hypofluorite ((CF 3 ) 3 C-OF) Perfluoro tert-butanol (4.2 g, 17.8 mmol) was prepared with carefully dried CsF (200 g). Condensed in a stainless steel container and allowed to reach room temperature. The mixture was thoroughly shaken before connecting the container to the steel line. At −78° C., elemental fluorine was added in portions until a pressure of 300 mbar was reached and no more fluorine was consumed. After an additional 20 minutes at -78°C, excess fluorine was removed while maintaining the vessel at -196°C.
実施例３：フッ化銀を用いた（ＣＦ３）３Ｃ－Ｏ－Ｏ－Ｃ（ＣＦ３）３の調製
実施例２からの反応混合物を、実施例１に従って新たに調製したフッ化銀触媒（２２ｇ）を入れた第２の鋼容器に蒸留した。－４５℃で５日後、ペルフルオロビス（ｔｅｒｔ－ブチル）ペルオキシドを反応容器から蒸留し、－７８°Ｃに保持された冷却トラップにトラップした（２．６ｇ、５．５ｍｍｏｌ、６２％）。
Example 3: Preparation of (CF 3 ) 3 C-O-O-C(CF 3 ) 3 using silver fluoride The reaction mixture from Example 2 was combined with a freshly prepared silver fluoride catalyst according to Example 1. (22 g) was distilled into a second steel vessel. After 5 days at −45° C., perfluorobis(tert-butyl) peroxide was distilled from the reaction vessel and trapped in a cold trap held at −78° C. (2.6 g, 5.5 mmol, 62%).
実施例４：ペルフルオロｔｅｒｔ－ブチルハイポクロライト（（ＣＦ３）３Ｃ－ＯＣｌ）の調製
ペルフルオロｔｅｒｔ－ブタノール（２．３６ｇ、１０ｍｍｏｌ）を、慎重に乾燥させたＣｓＦ（２００ｇ）を備えたステンレス鋼容器で凝縮し、室温に到達させた。容器をステンレス鋼ラインに接続する前に混合物を十分に振とうした。容器を液体窒素で冷却し、ガス状ＣｌＦ（１３ｍｍｏｌ）を添加した。反応混合物を０℃までゆっくりと温めた。１２時間後、混合物を頻繁に振とうしながら、混合物を－７８℃まで冷却し、過剰なＣｌＦを、ソーダライムで満たされたチューブを介して耐フッ素性ポンプシステムによって除去した。収量：９．２ｍｍｏｌ、９２％ハイポクロライト
Example 4: Preparation of perfluoro tert-butyl hypochlorite ((CF 3 ) 3 C-OCl) Perfluoro tert-butanol (2.36 g, 10 mmol) was added to stainless steel with carefully dried CsF (200 g). Condensed in a vessel and allowed to reach room temperature. The mixture was thoroughly shaken before connecting the vessel to the stainless steel line. The vessel was cooled with liquid nitrogen and gaseous ClF (13 mmol) was added. The reaction mixture was slowly warmed to 0°C. After 12 hours, the mixture was cooled to −78° C., with frequent shaking, and excess ClF was removed by a fluorine-resistant pump system via a tube filled with soda lime. Yield: 9.2 mmol, 92% hypochlorite
実施例５：ＵＶ照射下での（ＣＦ３）３Ｃ－Ｏ－Ｏ－Ｃ（ＣＦ３）３の調製
実施例４のハイポクロライト（１ｍｍｏｌ）を石英フラスコ（１Ｌ）に蒸留し、キセノン高圧ランプを使用して－７８℃で３０分間照射した。反応混合物のトラップトゥートラップ蒸留により、－７８℃トラップでペルフルオロビス（ｔｅｒｔ－ブチル）ペルオキシド（０．３ｍｍｏｌ、５７％）を得て、揮発性副生成物Ｃｌ２、（ＣＦ３）２ＣＯ及びＣＦ３Ｃｌを、－１９６℃に冷却されたトラップで収集した。
Example 5: Preparation of ( CF3 ) 3C -O-O-C( CF3 ) 3 under UV irradiation Hypochlorite (1 mmol) from Example 4 was distilled into a quartz flask (1 L) and heated under xenon high pressure. It was irradiated for 30 minutes at -78°C using a lamp. Trap-to-trap distillation of the reaction mixture yielded perfluorobis(tert-butyl) peroxide (0.3 mmol, 57%) in a −78° C. trap, with volatile byproducts Cl 2 , (CF 3 ) 2 CO and CF 3Cl was collected in a trap cooled to -196°C.
Claims (13)
Formula R 1 R 2 R 3 C-O-O-CR 4 R 5 R 6 where R 1 to R 6 are independently selected from the group consisting of F , CF 3 and C 2 F 5 A method for producing a compound comprising the step of reacting hypofluorites R 1 R 2 R 3 COF and R 4 R 5 R 6 COF with a mixture of AgF and AgF 2 .
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| IT1197472B (en) * | 1986-09-08 | 1988-11-30 | Ausimont Spa | PROCESS FOR THE PREPARATION OF PERALOHYDROCARBON HYPOCHLORITES |
| US20070049774A1 (en) | 2005-08-24 | 2007-03-01 | Syvret Robert G | Preparation of high purity fluorinated peroxides |
| EP2747092A1 (en) | 2012-12-21 | 2014-06-25 | Solvay SA | A method for dielectrically insulating active electric parts |
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